Conjugated polymers with stabilizing coordination units for single-site catalytic centers are excellent candidates to minimize the use of expensive noble metal electrode materials. In this study, conjugated metallopolymer, POS[Cu], was synthesized and fully characterized by means of spectroscopical, electrochemical, and photophysical methods. The copper metallopolymer was found to be highly active for the electrocatalytic hydrogen generation (HER) in an aqueous solution at pH 7.4 and overpotentials at 300 mV vs. reversible hydrogen electrode (RHE). Compared to the platinum electrode, the obtained overpotential is only 100 mV higher. The photoelectrochemical tests revealed that the complexation of the conjugated polymer POS turned its intrinsically electron-accepting (p-type) properties into an electron-donor (n-type) with photocurrent responses ten times higher than the organic photoelectrode.